ALKYL HALIDES, ALCOHOLS & ETHERS

KEY CONCEPTS

Types of solvents

Polar protic solvent Polar aprotic solvent

Capable of H-bonding Incapable of H-bonding

• even thought polar protic solvents are not the best SN2 and E2, these reactions are often run in these
solvents because nucleophiles and bases are often easily prepared in these solvents.
 Solvents Non Polar Polar Protic Aprotic
1. H2O ×   –
2. CH3OH ×   –
3. CH3CH2OH ×   –
4. H–COOH ×   –
5. CH3–COOH ×   –
6. NH3 ×   –
7. ×  × 

8. ×  × DMSO–Dimethyl sulphoxide

9. ×  × DMF – Dimethyl formamide

10. ×  × DMA – Dimethyl acetamide

11.   × 

12.   × 

13. C–C–C–C–C–C   × 
Organic Reagents
Organic reagents can be classified in two categories :
(1) Electrophile : Electron pair acceptor are electrophile.
(2) Nucleophile : Electron pair donor are nucelophile.

(1) Electrophiles
It can be classified into two categories :
(A) Charged electrophiles (E) (B) Neutral electrophiles (E)
(A) Charged electrophiles : Positively charged species in which central atom has incomplete
octet is charged electrophile

H  , X   R , , = O,

Note : Generally All cations are charged electrophiles except cations of A, A group elements,

Al+++ and .
(B) Neutral electrophiles : It can be classified into three categories :
(B) Neutral covalent compound in which central atom has incomplete octet is neutral
•• ••
electrophile, AlX 3, C H , C X 2 BF3, BCl3, BBr 3, BI3
2

(B) Neutral covalent compound in which central atom has complete or expended octet and
central atom has unfilled -d-shell is neutral electrophile
SnCl4, SiCl4, SbCl5
Note :
(i) Cl2, Br 2 and I2 also behave as neutral electrophiles.
(ii) Electrophiles are Lewis acids.

(2) Nucleophiles
Nucleophiles can be classified into three categories :
(A) Charged nucleophiles : Negatively charged species are charged nucleophiles.

, O , R – , C 3, , H, R–

(B) Neutral nucleophiles : It can be classified into two categories :

Neutral covalent compound, in which central atom has complete octet, has at least one lone
pair of electrons and all atoms present on central atom should not be electronegative, is
neutral nucleophile.
, R– , R2 , R3 , –NH2 (Nitrogen nucleophile)
H– –H, R– –H, R– –R (Oxygen nucleophiles)

H– –H, R– –H, R – – R (Sulphur nucleophiles)

H3, R H2, R2 H, R3 (Phosphorus nucleophiles)

(C) Ambident nucleophile : Species having two nucleophilic centres, one is neutral (complete
octet and has at least one lone pair of electrons) and other is charged (negative charge)
behaves as ambident nucelophile.

   –    

Note :
(A) Organometallic compounds are nucleophiles.
(B) Nucleophiles are Lewis bases.
 Organic compounds which behave as electrophile as well as nucleophile :
Organic compound in which carbon is bonded with electronegative atom (O, N, S) by multiple bond/
bonds behaves as electrophile as well as nucleophile.

O O O O
|| || || ||
R CH, R CR, R  C  OH , R  C  Cl

O O
|| ||
R  C  OR , R  C  NH2 , R–CN,

R– 
Note : During the course of chemical reaction electrophile reacts with nucleophile.

NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) AT SATURATED

CARBON

NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) :

Replacement (displacement) of an atom or group by an other atom or group in molecule is known as
substitution reaction. If substitution reaction is brought about by a nucleophile then it is known as
nucleophilic substitution reaction. Generally substitution takes place at sp3 carbon.
R–g +  R – Nu +

UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTIONS (SN1) :

Nucleophilic substitution which involves two step process
(a) First step : - Slow step involves ionisation to form carbocation
R–g  R+ + g –
(b) Second step : - Fast attack of nucleophile on carbocation to result into product .
R+ + Nu –  R–Nu
SN1 Reaction of Alkyl halide

Mechanism :

Ionisation of
alkyl halide
    
Slow step (rds)

Characteristics of SN1 reactions :

1. It is unimolecular, two step process.
2. Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
3. It is first order reaction
4. Kinetics of the reaction Rate  [Alkyl halide]

Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.

 5. Energetics of the SN1

Figure : Free energy diagram for the SN1 reaction.

SN1 Reaction of Alcohols

(A) Reaction with hydrogen halides
A common method is to treat the alcohol with a hydrohalic acid, usually HI or HBr. These acids are
used to convert alcohols to the corresponding alkyl halides.
(i) In acidic solution, an alcohol is in equilibrium with its protonated form. Protonation converts the
hydroxy group from a poor leaving group to a good leaving group (H2O). If the alcohol is
protonated all the usual substitution and elimination reactions are feasible, depending on the struc-
ture (1°, 2°, 3°) of the alcohol.
(ii) Halides are anions of strong acids, so they are weak bases. Solutions of HBr and HI contain
nucleophilic and ions.
(iii) Concentrated hydrobromic acid rapidly converts t-Butyl alcohol to t-Butyl bromide. The strong acid
protonates the hydroxyl group, converting it to a good leaving group. The hindered tertiary carbon
atom cannot undergo SN2 displacement, but it can ionise to a tertiary carbocation. Attack by
bromide ion gives the alkyl bromide. The mechanism is similar to other SN1 mechanism.
(iv) 1-Butanol reacts with sodium bromide in concentrated sulfuric acid to give 1-Bromobutane by an SN2
displacement.
NaBr, H SO
2 4
CH3 (CH2 )2  CH2 OH     
  CH3 (CH2 )2  CH2Br
1  bu tan ol 1  bromobutane
(90%)
Protonation converts the hydroxy group to a good leaving group, but ionization to a primary carbocation
is unfavourable. The protonated unbranched primary alcohol is well suited for the SN2 displacement.
(v) Secondary alcohols also react with HBr to form alkyl bromides usually by the SN1 mechanism.

e.g. HBr


(vi) HCl (Hydrochloric acid) reacts with alcohols in much the same way that as the hydrobromic acid.
(vii) Chloride ion is a weaker nucleophlile than bromide ion because it is smaller and less polarizable.
Lewis acid, such as ZnCl2, is sometimes necessary to promote the reaction of HCl with primary and
secondary alcohols.
 Mechanism :
 RDS 
R –OH R  O H2   R
–H2O R – X

Reactivity of HX : HI > HBr > HCl

Reactivity of ROH : allyl  benzyl > 3° > 2° > 1°

SN1 REACTIONS OF ETHERS

(A) Reaction with HX
Ethers are unreactive towards most bases, but they can react under acidic conditions. A protonated
ether can undergo substitution or elimination with the expulsion of an alcohol. Ethers react with conc.
HBr and HI because these reagents are sufficiently acidic to protonate the ether, while bromide iodide
are good nucleophiles for the substitution.
If R or R’ is 3º then mechanism will be SN1 otherwise SN2 .

Mechanism :

X
R – O – R`     R` – X
– ROH

SN2 Reaction of Alkyl halide :

Mechanism :  +

Characteristic of SN2
1. It is bimolecular, one step concerted process
2. It is second order reaction because in the rds both species are involved
3. Kinetics of the reaction  rate  [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic
substitution reaction is double. If the concentration of nucleophile is doubled the rate of reaction is
also double. If the concentration of both are doubled then the rate of the reaction quadriples.
4. Energetics of the reaction :

Figure : A free energy diagrams for SN2 reaction

5. No intermediates are formed in the SN2 reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.
 6. The stereochemistry of SN2 reactions  As we seen earlier, in an SN2 mechanism the nucleo-
phile attacks from the back side, that is from the side directly opposite to the leaving group. This
mode of attack causes an inversion of configuration at the carbon atom that is the target of
nucleophilic attack. This inversion is also known as Walden inversion.

Inversion
  

SN2 Reaction of Alcohol

(A) Reaction with HX : The protonated  unbranched primary alcohol is well suited for the SN2 reaction.
Mechanism :
 X
R –OH R  O H2  R – X + H2O

CH3 CH2 CH2 CH2 CH2Cl

e.g CH3 CH2 CH2 CH2CH2OH
n  Pentyl alcohol n  Pentyl chloride

(B) Reaction with phosphorus trihalides

Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, & PCl5 work
well and are commercially available.
Phosphorus halides produce good yields of most primary and secondary alkyl halides, but none works
well with tertiary alcohols. The two phosphorus halides used most often are PBr3 and the P4/I2 combi-
nation.

3R – OH + PX3 3R – X + H3PO3
Mechanism :

Step : 1

Step : 2 RCH2X+ HOPX2

Remarks
The mechanism for the reaction involves attack of the alcohol group on the phosphorus atom, displacing
a halide ion and forming a protonated alkyl dihalophosphite
In second step a halide ion acts as nucleophile to displace HOPX2, a good leaving group due to the
electronegative atoms bonded to the phosphorus.

(C) Reaction with thionyl chloride in presence of pyridine

Thionyl chloride (SOCl2) is often the best reagent for converting an alcohol to an alkyl chloride. The by
products (gaseous SO2 and HCl) leave the reaction mixture and ensure that there can be no reverse
reaction.
O
||
Heat
R – OH + Cl  S  Cl    R – Cl + SO2 + HCl
Pyridine
 Mechanism :

..
– H .. .. O:
  R – O + HCl
.. – S
Cl
Chlorosulphite ester

 R – Cl + SO2

In the first step, the nonbonding electrons of the hydroxy oxygen atom attack the electrophilic sulphur
atom of thionyl chloride. A chloride ion is expelled a proton and gives test of chloro sulphite ester.
Second step is an SN2 mechanism

SOCl 2
e.g.   

Py

Reaction with thionyl chloride

ROH + SOCl2  RCl + SO2 + HCl
In this mechanism an internal nucleophile attacks from the same side of leaving group , means retension
of configuration . It is an SNi mechanism , where i means internal

Mechanism :

..
– H .. .. O:
  R – O + HCl
.. – S
Cl
Chlorosulphite ester

 R – Cl + SO2

e.g.

SN2 Reaction of Ether

(A) Reaction with HX
A protonated ether can undergo substitution reaction. Ether react with conc. HBr and HI because these
reagents are sufficiently acidic to protonate the ether. If R or R’ is 3º then mechanism will be SN1
otherwise SN2.
 Mechanism :

HX
+  X R +  X – R + X – R
alkyl halide

SN Reaction of Epoxide
Epoxides are much more reactive than ether because of angle strain in three membered ring therefore
epoxide readily undergo nucleophilic substitution reaction.

In basic medium mechanism is SN2. Nucleophile atacks on less hindered carbon.

Mechanism :

Nu
| Nu
R — CH — CH2 
H |
 R — CH — CH2
| |
O OH

e.g.

In acidic medium mechanism is SN1 type. Nucleophilic attacks on more substituted carbon.

Mechanism :

Nu

|
H

 R — CH — CH2
|
OH

ELIMINATION REACTIONS :
E1 Reaction :
Proton and leaving group depart in two different step.
(a) First step : - Slow step involves ionisation to form carbocation
(b) Second step : Abstraction of proton

Mechanism :

Step 1 : Formation of the carbocation (RDS)

 Step 2 : Base ( ) abstracts a proton (fast)

+ B – H

E2 Reaction :
Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene.
(i) Hot alcoholic solution of KOH, EtO¯/EtOH
(ii) NaNH2

(iii) t-BuO¯ K in t-BuOH
This is one step reaction, hydrogen and leaving group depart simultaneously
Mechanism :

  + BH

(iii) E1 cB Reaction (Unimolecular conjugate base reaction) 

In the E1 cB, H leaves first and then the X. This is a two step process, the intermediate is a
carbanion.
Mechanism :

Step - 1: Consists of the removal of a proton, , by a base generating a carbanion

H
| |
CC X
| |

Step - 2: Carbanion looses a leaving group to form alkene

 –C  C –
| |
Condition : For the E1 cB, substrate must be containing acidic hydrogens and poor leaving groups.
 EXERCISE - 1
1. K1
(i) CH3–CH2–Br + NaOH  CH3–CH2–OH + NaBr  reaction —— (i)

(ii) K2
+ NaOH 
 (CH3)3C—CH2–OH + NaBr reaction —— (ii)

K1 & K2 are rate constant for above reaction. Correct relation is :

(A) K1 = K2 (B) K1 > K2 (C) K1 < K2 (D) K1 < < K2

2. Free energy profile for given reaction is 

(A) (B)

(C) (D)

3. Rate expression for reaction 

(A) rate = K [CH3–Br] (B) rate = K[HO] [CH3–Br]
(C) rate = K[HO] (D) rate = K[HO]2 [CH3–Br]

4. (A), Major-Product (A) is :

(A) (B) (C) (D)

5. (A), Product (A) is

(A) (B) (C) (D)

6.

Which of the following figures represent correctly the structure of transition state in this reaction ?

(A) (B)

(C) etiher (A) or (B) depending upon situation (D) none of these

7. Which of the following reactions is not possible ?

(A) R–OH + NaBr  R – Br + NaOH (B) R – OH + HBr  R – Br + H2O
(C) both reactions are possible (D) both reactions are not possible

8. , ,

Which of the following orders is correct about leavelability of these groups in nucleophilic substitutions:
(A) I > II > III (B) III > II > I (C) III > I > II (D) II > III > I

9. Which of following compounds will not undergo acid catalysed hydrolysis ?

(A) (B) (C) (D)

10. Which of the following ethers is unlikely to be cleaved by hot conc. HBr ?

(A) (B) (C) (D)

11. The reaction of CH3OC2H5 with one mole HI gives :

(A) CH3OH (B) C2H5OH (C) CH3I + C2H5OH (D) C2H5I + CH3OH

12.

Product of above reaction is :

(A) and CH3OH (B) & CH3I

(C) and CH3I (D) & CH3OH

13.

SN2 reactivity of these substrate, under identical conditions, will be in the order as :
(A) I > II > III (B) III > II > I (C) III > I > II (D) II > III > I

14. A gem dichoride is formed in the reaction except :

(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5

(C) (D)

15. From each of the following pairs select the compound that will react faster with sodium iodide in acetone.
(a) 2-Chloropropane or 2-bromopropane
I II
(b) 1-Bromobutane or 2-bromobutane
I II
(A) (a)-I, (b)-I (B) (a)-I, (b)-II (C) (a)-II, (b)-I (D) (a)-II, (b)-II

16. , A is :

(A) (B) (C) Both A & B (D)

17. Which of the following nucleophile will show minimum reactivity towards SN2 reaction :

(A) (B) (C) (D)

18.

(A) (B) (C) (D)

19. Which of the following compounds will show NGP ?

(A) (B) (C) (D)

20.

Value of x in above reaction is :

(A) 2 (B) 3 (C) 4 (D) 5
21.

x = moles of HI consumed value of x is :

(A) 2 (B) 4 (C) 5 (D) 6

22. Consider the reaction of HI with the following :

(I) (II)

Which forms di-iodide on reaction with HI (excess) ?

(A) I and Ii both (B) II only (C) I only (D) none

23. (A)

Major-product (A) is :

(A) (B) (C) (D)

24. (A), Product (A) in

(A) (B) (C) (D)

25. SN1 is a two-step reaction. For each step, there has to be a transition state. Which of the following structures
represent correctly the transition state of first step :

(A) R   .....L –  
(B) R  – .....L   
(C) R   .....Nu  –  
(D) R  – .....Nu   

26. products are

(A) + EtOH (B) + EtOH

(C) + EtOH (D) +

27. Under identical considitions, solvolysis of which of the following substrates would lead to maximum recemization?

(A) (B) (C) (D)

28.

Structure of X is :

(A) (B) (C) (D)

29. The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because :
(A) Alkyl chlorides are immiscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction does not occur via intermediate formation of an alkyl chloro sulphite

30. Which of the following alcohol shows fastest reaction with HI ?

(A) (B) (C) (D)

31. Which one of the following compounds will be most reactive for SN1 & SN2 reactions :

(A) (B) (C) (D)

32. Which one of the following compounds will give enantiomeric pairs on treatment with HOH ?

(A) (B) (C) (D)

33. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction.

(I) (II)

(III) (IV)

(A) II > III > IV > I (B) IV > III > II > I
(C) III > IV > II > I (D) I > II > III > IV
34. For the given reaction ;

Which substrate will give maximum racemisation ?

(A) (B)

(C) (D)

35. In the given reaction : [X]

(A) (B) (C) (D)

36. Among the bromides I-III given below, the order of reactivity of SN1 reaction is :

(I) (II) (III)

(A) III > I > II (B) II > III > I (C) II > III > I (D) II > I > III

37. Which of the following compounds is most rapidly hydrolysed by SN1 mechanism
(A) C6H5Cl (B) Cl–CH2–CH=CH2 (C) (C6H5)3CCl (D) C6H5CH2Cl

38. Which will give white ppt. with AgNO3 ?

(A) (B) (C) (D) Both A & C

39. When ethyl bromide is treated with moist Ag2O, main product is :
(A) Ether (B) Ethanol (C) Aldehyde (D) All of the above

40. A, A is :

(A) (B) (C) (D)

41.

Products of above reaction is :

(A) (B)

(C) (D)

42.

Value of (x) is :
(A) 1 (B) 2 (C) 3 (D) 4

43. Best method for preparation of by williamson’s ether synthesis is :

(A) (B)

(C) (D)

44. In the given reaction : [X], [X] will be :

(A) (B)

(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)

45. In the given reaction [X], [X] will be :

(A) (B)

(C) (D)
46. Products are :

(A) (B) (C) (D)

47. Which of the following carbocation is most stable :

(A) (B)

(C) (D)

48. Which of the following carbocation will undergo rearrangement ?

(A) (B)

(C) (D)

49. A less stable carbonium ion rearranges to a more stable carbonium ion. During this rearrangement migrating
atom or group leaves as a :
(A) Free radical (B) Carbene
(C) Positively charged ion (D) Negatively charged ion

50. (B), give structure of (B) :

(A) (B) (C) (D)

51. Arrange the following compounds in the increasing order of their densities :

(a) (b) (c) (d)

(A) (a) < (b) < (c) < (d) (B) (a) < (c) < (d) < (b) (C) (d) < (c) < (b) < (a) (D) (b) < (d) < (c) < (a)

52. SN1 + E1 products. The total number of products are :

(A) 5 (B) 6 (C) 7 (D) 8

53.

(A) (B) (C) (D)

54.

(A) (B) (C) (D)

55. (A) (B)

Product (B) will be :

(A) (B) (C) (D)

Cl
56. n-Penten 
2
 (A)
h

Mono-chloro product (including streoisomers) are :

(A) 2 (B) 3 (C) 4 (D) 5

57. ?

(A) (B) (C) (D)

58. (A) (B)

(B) is

(A) (B) (C) (D) None of these

59. ? Possible products are :

(A) (B)

(C) (D) All of these

60. (I) (II)

(III) (IV)
Correct order of rate of reaction will be
(A) IV > III > I > II (B) III > IV > I > II (C) IV > I > III > II (D) None of these

61. Pick the correct statement for monochlorination of R-secbutyl chloride.

Cl2


300C

(A) There are four possible products ; three are optically active one is optically inactive
(B) There are five possible products ; three are optically inactive & two are optically active
(C) There are five possible products ; three are optically inactive & three are optically active
(D) There are four possible products ; two are optically active & two are optically inactive

Cl2
62. Reaction-1 : CH3–CH2–CH2––CH2–CH3 
 Optically active monochloro product(s) are (R).
h

Cl2
Reaction-2 :  Optically active di-chloro product(s) are (S).

h

Cl2
Reaction-3 :  Optically active di-chloro product(s) are (P).

h

Cl2
Reaction-4 : 2-methoxy propane 
 Optically active mono chloro product(s) are (Q).
h
Sum of P + Q+ R+ S is
(A) 8 (B) 9 (C) 10 (D) 11

Cl2
63.  (X) DCP

h

X is :
 (A) 5 (B) 7 (C) 9 (D) 11

Cl2
64. 
 (X) monochloro product
h

(A) 6 (B) 8 (C) 9 (D) 10

Cl2
65. 
 (X) Product
h

X is (x is monochloroproduct)
(A) 4 (B) 6 (C) 9 (D) 10

Cl2
66. 
 (X) Di-chloro product
h

(A) 5 (B) 6 (C) 7 (D) 8

Cl2
67. 
 (X) mono chloro product
h

(A) 2 (B) 3 (C) 4 (D) 5

68. In which of following reaction diastereomer will form

Br2 Br2
(A) Cl2
 (B)
  (C)  (D) All
h h h

69.

Above is energy profile for r.d.s of

(A) lodination of alkane (B) Chlorination of alkane
(C) Bromination of alkane (D) Cannot predict

70. Which of the following reaction has (Ea = H).


(A) Cl• + H – CH3  HCl + CH3 (B) Cl• + Cl•  Cl2

h 
(C) Cl2  2Cl (D) Et• + H – CH3  Et–H + CH3

71. Which of following reaction has (Ea = 0)


(A) Cl• + H – CH3  HCl + CH3 (B) Cl• + Cl•  Cl2

h 
(C) Cl2  2Cl (D) Et• + H – CH3  Et–H + CH3
 D2
72. 
 Product will be :
Pt

(A) (B) (C) (D) B & C both

Na Cold KMnO 4
73. CH3–C  C – CH3  ( A )      (B)
liq.NH3

(A) Meso (B) Recemic mixture (C) Diastereomers (D) All

H2 Br2
74. CH3–C  C – CH3   ( A ) (B)
PdBaSO4 CCl4

(A) Meso (B) Recemic mixture (C) Diastereomers (D) All

Na Br2
75.  ( A ) 
CH3–C  C – CH3  (B)
liq.NH3 CCl4

(A) Meso (B) Recemic mixture (C) Diastereomers (D) All

HCl
76.   (x) (major product)
Peroxide

Structure of (x) will be

(A) (B) (C) (D)

77. 1-Penten-4-yne reacts with bromine at –80°C to produce :

(A) 4, 4, 5-Tetrabromopentene (B) 1,2-Dibromo-1, 4-pentadiene
(C) 1, 1, 2, 2, 4, 5-hexabromopentane (D) 4, 5-dibromopentyne

BD
78. CH3–CH = CH2 2
6


product X, X is -
H2O2 / OH

(A) (B) (C) (D) None of these

BH3 .THF
79.   
H2O2 / OH

(A) (B) (C) (D)

80. A, A is :

(A) (B) (C) (D)

81. Major product will be :

(A) (B) (C) (D) All

82. Which mechanism best accounts for the transformation in the brackets ?

(A) (B)

(C) (D)

83. Consider the following rearrangement reaction

Which of the following reaction coordinates best represents the overall reaction ? (Note : the units are
arbitrary)

(A) (B) (C) (D)

84. P (major)

(A) (B) (C) (D)

85.
Thermodynamically controlled product will be :

(A) (B) (C) (D)

86. (A) C4H10O (B) C4H10O

What is relationship between A & B ?
(A) A and B may be position isomer (B) A and B may be chain isomers
(C) A and B may be stereoisomers (D) All of the above

87. The product(s) of the following reaction can best be described as :

(A) A racemix mixture (B) A single enantiomer

(C) A pair of diastereomers (D) An achiral molecule

88. Major product obtained in the following reaction r1, r2 and r3 in respectively is :

(A) , , (B) , ,

(C) in all reaction (D) in all reaction

89. The reaction of HBr with the following compound would produce :

(A) (B)

(C) (D)
90. In which of the following reaction formation of racemic mixture :

(A) (B)

(C) (D)

91. Which reaction condition would be best to perform the following transformations ?

(A) NBS, MeOH (B) OsO4, HBr, NaOH, Mel

(C) Br2/H2O (D) mCPBA, HBr, NaOH Mel

92.* (x)
Stereochemistry of product will be :
(A) Optically active (B) Optically inactive
(C) Racemic mixture (D) meso

93.* + Br

Correct statement regarding above reaction is :

(A) Alkene will act as HOMO (Highest Occupied Molecular orbital).
(B) Br2 will act as LUMO (Lowest unoccupied molecular orbital).
(C) Br2 will act as SOMO (Single occupied molecular orbital).
(D) Overall mechanism is anti addition.

94. CH3—CC–CH3 (A) (B). Product (B) of above reaction is :

(A) (B) (C) (D)

BH3THF HgSO 4 / H2SO 4

95. B    CH3–CCH     A, A and B are -
H2O2 ,OH

(A) (B)
(C) CH3CH2CHO (both) (D)

HgSO HgSO4
96. CH3–CCH  
4
 (A) ; CH3–CC–CH3    (B)
H2SO4 H2SO4

Relation between (A) & (B)

(A) Position isomers (B) Functional isomers
(C) Homologous (D) Metamers
 H2 ( one mole )
97.    Product will be :
Pt

(A) (B) (C) (D) B and C both

98. What is the major organic product of the following reaction ?

2
Hg
 
H2SO 4

(A) (B)

(C) (D)

99. The product obtained via oxymercuation (HgSO4 + H2SO4) of 1-butyne would be-
(A) (B) CH3–CH2–CH2–CHO

(C) CH3–CH2–CHO + HCHO (D) CH3–CH2–COOH + HCOOH

100. Intermediate produced when propene react with HCl in presence of peroxide :
 
(A) CH3  CH2  CH2 (B) CH3  CH  CH3

 
(C) CH3  CH2 CH2 (D) CH3  CH CH3

EXERCISE - 2

 
1. AcO Na
   (A)
Major product (A) is

(A) (B)

(C) (D)

2. In the acid catalyzed dehydration of alcohols to alkenes, the intermediate species formed is-
(A) Free readical (B) Carbocation (C) Carbanion (D) Carbene

3.

Value of x is
(A) 1 (B) 2 (C) 3 (D) 4
 alc.KOH
4.   X (major)


(A) (B) (C) (D) None of these

5. The energy profile of the given reactions :

(A) (B) (C) (D)

6. (X).

Major product (X) is :

(A) (B) (C) (D)

7. Which of the following alcohols would be most likely to undergo dehydration with rearrangement by a process
involving a methyl migration (methyl shift only) ?

(A) (B) (C) (D)

8. X, X is :

(A) (B) (C) (D)

9. Rate of dehydration when given compound is treated with conc. H2SO4

(P) (Q) (R) (S)

(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P
10. Among the given compounds, the correct dehydration order is :

(I) (II) (III) (IV)

(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < II < III = IV

11. A Final product A is :

(A) (B) CH2=C=CH2 (C) (D)

12. A Product A is :

(A) (B) (C) (D)

13. Which of these dehydrates most readily when reacts with conc. H3PO4.

(A) (B) (C) (D)

14. (P) (Major), Major product (P) is :

(A) (B) (C) (D)

15. A, A is :

(A) (B)

(C) (D)
 alc.KOH
16.   major product is :


(A) (B) (C) (D)

17. Which of following halides gives fastest elimination reaction when it is treated with alcoholic KOH.

(A) (B) (C) (D)

18. Which of following is dehydrating agent ?

(A) Conc. H3PO4 (B) P2O5 (C) POCl3 (D) All

Comprehension (Q.19 to Q.22)

(A) (B) (C) (D) CH3–Cl

19. Most reactive towards SN1 reaction

20. Most reactive towards SN2 reaction ?

21. Most reactive towards E2 reaction ?

22. Most reactive towards E1 reaction ?

EXERCISE - 3
Choose the correct option, Only one correct

1.

Identify all possible product obtained by E2 reaction ?

(A) (B)

(C) both (A) and (B) (D) None of these


H Br2
2.  ( A ) 
  (B)
 major CCl4

Product (B) is :
(A) meso (B) Racemic (C) Diastremer (D) optically active single
3.

The reaction is a case of

(A) -elimination (B) -elimination (C) -elimination (D) none of these

4. Most reactive towards acid-catalyzed hydrolysis is

(A) (B) (C) EtOEt (D) EtOH

5.

Total number of products obtained when this substrate is subjected to E2 reaction will be (including stereoisomer)
(A) 3 (B) 4 (C) 5 (D) 6

6.

The major products obtained when this substrate is subjected to E2 reaction will be

(A) (B) (C) both (A) and (B)(D) none of these

7.

The major product obtained when this substrates is subjected to E2 reaction under the treatment of potasium
tert-butoxide will be

(A) (B)

(C) both is equal proportions (D) none of these

8. I II III

Ease of -dehydrobromination among these substrates under the treatment of strong base will be in the order
(A) I > II > III (B) III > II > I (C) II > I > III (D) II > III > I
9. Which of the following cannot undergo and E2 reaction ?

I II III

(A) I (B) II
(C) III (D) None (all can undergo an E2 reaction )

Alc .KOH
10. Major product of the reaction is  

(A) Butene-1 (B) Trans-2-butene (C) cis-2-butene (D) Butyne-1

11. Which of the following expression is the experimentally observed rate law for an E2 reaction of an alkyl halide
(A) Rate = k[RX] (B) Rate = k[RX]2 (C) Rate = k[RX] base (D) Rate = k[base]

12. Which alkyl bromide will yield only one alkene upon E2 elimination ?

(A) (B) (C) (D)

13. Which alkyl bromide will yield-3-methyl-1-hexene as the major product upon treatment with potassium t-
butoxide in t-butyl alcohol (solvent) ?

(A) (B) (C) (D)

14. In order to accomplish the following conversion, what reagent and conditions would be required ?

(A) Cold sodium hydroxide (B) Hot conc. sodium hydroxide

(C) Potassium t-butoxide and heat (D) Hot water

15.

Which is most easily dehydrohalogenated ?

(A) I (B) II (C) III (D) All with same ease

CH3OH
16. CH3O – CH = CH2  
 product formed is
H
(A) Acetal (B) Hemiacetal (C) Alcohol (D) Aldehyde

17.

Total number of SN1 products of given compound are

 (A) 3 (B) 4 (C) 5 (D) 6

18.

Total number of SN1 + E1 products obtained will be-

(A) 5 (B) 6 (C) 7 (D) 8

  
H H H
19. 
 (A) ; 
 (B) ; 
 (C)
  

Stability of product (A), (B), (C) is :

(A) C > B > A (B) A > B > C (C) B > C > A (D) C > A > B

20.

The major product obtained this substrate is subjected to E2 reaction will be

(A) (B) (C) both (A) and (B) (D) None of these

21. Which of the following isomeric hexachlorocyclohexanes is least reactive in -dehydrochlorination on treatment
with strong base ?

(A) (B) (C) (D) all three are equally react

22. If the following E2 reaction proceeds through an anti-periplanar transition state, what product or product
excepted ?

(A) Only-3-methylcyclohexene
(B) Only-1-methylcyclohexene
(C) The major product is 3-methylcyclohexene and the minor product is 1-methyl cyclohexene
(D) The major product is 1-methylcyclohexene and the minor product is 3-methyl cyclohexene

23. The nitrogen atom in each of the following tertiary amines may be removed as trimethyl amine repeated
Hofmann elimination (exhaustive methylation followed by heating with AgOH). Which of the amines requires
the greater number of Hofmann sequences to accomplish this ?
 (A) (B) (C) (D)

24. Correct order of yield of Hofmann alkene in following reaction will be

X may be F, Cl, Br or I

(A) F > Cl > Br > I (B) I > Br > Cl < F (C) Cl > F > Br > I (D) I > Br > F > Cl

25.   ? Major product is :

Br2

(A) (B) (C) both (A) & (B) (D) none of these

alc.KOH EtONa
26.   X ;   Y +

Major  Major

Product (X) & (Y) respectively is

(A) 1-butene, trans-2-butene (B) 1-butene, cis-2-butene
(C) cis-2-butene, 1-butene (D) trans-2-butene, 1-butene

27. Predict the major product of the following reaction :

H2SO4
 

heat

(A) (B) CH3CH=C(CH3)2

(C) CH3CH=CHCH2CH3 (D) (CH3)2CHCH = CH2

28.

The major product obtained when this substrated to E1 reaction will be

(A) (B) (C) (D) none of these

29. Conc .H2SO 4

   major product having H

(A) 12 H (B) 8 H (C) 4 H (D) 11 H

 EXERCISE - 4
ADVANCE LEVEL PROBLEM
Choose the correct option, One or more than one are correct
1. Which of the following compound will not undergo Nucleophilic substitution reaction.

(A) (B) (C) (D)

2. Consider the given reaction :

Which of the following statements are correct for above reaction

(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is SN2
(C) The reaction is SN1
(D) Configuration of products is (R)

3. Rate of SN2 will be negligible in

(A) (B) (C) (D)

4. Which are possible products in following

moist Ag2O
  
SN 1

(A) (B) (C) (D)

5. SN1 & SN2 product are same in (excluding stereoisomer)

(A) (B) (C) (D)

6. Statement-1 : On moving 1° to 3° alkyl halide rate of E2 increases while rate of SN2 decreases.
Statement-2 : E2 reaction give elemental effect with respect to halogen
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1
(C) Statement-1 is true, statement-2 is false
(D) Statement-1 is false, statement-2 is false.
PCl5
7. CH3–CH2–O–CH3  
 Product are:

(A) CH3–Cl (B) Et–Cl (C) (D)

8. PCl5
 product are

(A) (B) (C) (D) Ph–CH2–CH2

9. Zn dust
(p)  
Compound (p) is

(A) (B) (C) (D)

10. Zn dust
  (p). The product (p) is

(A) (B) (C) (D)

Paragraph for Question No. 11 to 13 (3 questions) :

Dehydration requires an acid catalyst to protonate the hydroxy group of the alcohol and convert in to going
leaving group. Loss of water followed by a loss of a proton, given the alkene an equilibrium is established
between reactants and products.

Mechanism

11. To improve the yield of above reaction which of following is correct.

(A) High temperature (B) Distillation
(C) Addition of H2O (D) Both (A) and (B)

 
H H
12. (i) 
 (A) Major (ii) 
 (B) Major
 
 
H
(iii) 
 (C) Major


total number of -hydrogen in A + B + C is

(A) 23 (B) 25 (C) 37 (D) 29

13. Which alcohol is most reactive towards dehydration of alcohol in acid catalyzed reaction.

(A) (B) (C) (D)

Matrix

14. Column - I Column - II

Primary alkyl bromide SN2 relative rate

(A) CH3–CH2–Br (P) 10–5

(B) Me–CH2–CH2–Br (Q) 10–2

(C) (R) 0.8

(D) (S) 1

15. Column - I Column - II

Alkyl–P–toluene solfonate Ethanolysis relative rate (50°C)

(A) CH3–CH2–OTs (P) 1010

(B) H2C=CH–CH2–OTs (Q) 105

(C) Ph–CH2–OTs (R) 400

(D) (S) 35

(E) Ph3C–OTs (T) 1

16. Substrate E2 elimination SN2 - substitution

(A) CH3–CH2–Br (P) 1 (W) 0

(B) (CH3)2CH–Br (Q) 80 (X) 20

(C) (CH3)3CBr (R) 100 (Y) 90

17. Reaction Relative rate of reaction

(A) HO + R – CH2 – I  (P) 1
(B) HO + R – CH2 – Br  (Q) 200
 (C) HO + R – CH2 – CI  (R) 10,000
(D) HO + R – CH2 – F  (S) 30,0000

18. Column - I Column - II

Alkyl bromide Relative rate of SN2

(A) (P) 1

(B) (Q) 11.6

(C) CH3–CH2–Br (R) 1,200,000

19. Column - I Column - II

Solvent Relative rate of SN2

(A) 100 % water (P) 1200

(B) 80 % water + 20 % ethanol (Q) 400

(C) 50 % water + 50 % ethanol (R) 60

(D) 20 % water + 80 % ethanol (S) 10

(E) 100 % ethanol (T) 1

20. Match List-I with List-II for given SN2 reaction & select the correct answer from the codes given below :
Z – CH2Br + CH3O  Z –CH2–OCH3 + Br
List - I List - II (relative reactivity)

(A) H– (P) 0.1

(B) CH3– (Q) 3

(C) C2H5– (R) 1

(D) (S) 100

21. Match List-I with List-II and select the correct answer from the codes given below :
List - I List - II

(A) CH3–O–SO2CH3 + C2H6O (1) CH3–CH2–PH2

(B) CH3–CH2–I + PH3 (2) CH3–O–C2H5


(C) HC  C N a  CH3  CH2  Br (3) CH3–O–CH3


(D) CH3–Cl + CH3– O (4) CH  C–CH2–CH3

22. Column-I and Column-II contains four entries each. Entrie of column-I is to be matched with some entry of
column-II. One or more than one entries of column-I may have the matching with the same entrie
column-II and one entry of column-I may have one or more than one matching with entries of column-II
Column - I Column - II
 EtOH
(A)   (P) SN2 reaction


(B) EtO (Q) E1 reaction
 
EtOH

CH3OH
(C)   (R) E2 reaction


(D) (S) SN1 reaction

DMF
23. Nu  Me  OTs  Me  Nu  TsO
25
This is an SN2 reaction where nucleophile attackes Me–OTs in the rate determining step. Rate of this
reaction increases with concentration as well as nucleophilicity of the nucleophilie. Match the column-I with
column-II for the above reaction
Column - I Column - II
(Nucleophilie) (Relative rate)
(A) F (P) 3.25

(B) Cl (Q) 6.25

(C) Br (R) 1.0

(D) I (S) 7.75

24. Match List-I with List-II (no. of structural isomers produced in -E2 elimination) and select the correct answer.
List - I List - II

(a) (i) Three

(b) (ii) Zero

(c) (iii) One

(d) (iv) Two

(a) (b) (c) (d) (a) (b) (c) (d)

(A) (i) (ii) (iv) (iii) (B) (iv) (iii) (i) (ii)
(C) (iv) (iii) (ii) (i) (D) (i) (iii) (iv) (ii)
25. Match the column
Column - I Column - II
 (A) (W) One of product is Ph–OH

(B) (X) One of product is CH3–CHO

(C) (Y) One of product is 2° alcohol

(D) (Z) No-reaction

26. Column - I Column - II

(A) (P) No-reaction

(B) (Q)

is one of the product of the reaction

(C) (R)

is one of the product of the reaction

(D) (S)

is one of the product of the reaction

27. Column - I Column - II
 (A) (P) Pinacol type reaction

(B) (Q) Pinacolic Diazotization reaction

(C) (R) Pinacol-Pinacolone reaction

(D) (S) Product formed is

(T) Semipinacol reaction

28. Column - I Column - II

(A) Best leaving group (P) F

(B) Best nucleophile in polar protic solvent (Q) Cl

(C) Best nucleophile in polar aprotic solvent (R) Br

(D) Weakest base (P) I

29. Substitution Logistics :

You were asked to run a series of reactions in the lab with different experimental conditions. Based on the
experimental observation you gathered (listed below),. indicate which mechanism this evidence supports.
(Check the appropriate box to correspond to your answer.

S.No. Observation SN1 S N2 Both

The rate of the reaction decreased when the concentration of the Nu is
1
decreased.
The rate of the reaction increased when the concentration of the RX was
2
increased
3 The rate of increased when the X was changed from Cl to I.

4 The products showed a skeletal rearrangement.

5 The product showed inversion of configuration

The Nu was changed from methoxide to isopropoxide and the rate
6
decreased
The RX was changed from 2° alkyl halide to a 2° allyl halide and the rate
7
increased
8 The solvent was switched from ethanol to acetone and the decreased
 EXERCISE - 5 : PREVIOUS YEAR JEE MAINS QUESTIONS

1. The product of the reaction given below is : (2016)

(c) (d)

5. Which one of the following reagents is not suitable for

the elimination reaction ? Online 2016 SET (2)

(a) (b)
(a) NaOH/H2O (b) NaOEt /EtOH
(c) NaOH /H2O  EtOH
(d) NaI
6. Fluorination of an aromatic ring is easily accomplished
(c) (d) by treating a diazonium salt with HBF4 . Which of the
following conditions is correct about this reaction ?
Online 2016 SET (2)
2. The reaction of propene with HOCl (a) Only heat (b) NaNO2 / Cu
(Cl2 + H2O) proceeds through the intermediate : (2016) (c) Cu2O / H2O (d) NaF/Cu
7. Which of the following compounds will not undergo
(a) CH3  CH  CH2  Cl Friedel Craft’s reaction with benzene ?
Online 2017 SET (1)
(b) CH3  CH(OH)  CH2

(c) CH3  CHCl  CH2

(d) CH3  CH  CH2  OH

3. The gas evolved on heating CH3MgBr in methanol is :
Online 2016 SET (1)
(a) HBr (b) Methane 8. The major product of the following reaction is :
(c) Ethane (d) Propane
4. Bromination of cyclohexene under conditions given below
yields : Online 2016 SET (2)

Online 2017 SET (1)

(a) CH2 = CHCH2CH = CHCH3
(b) CH2 = CHCH = CHCH2CH3
(c) CH3CH = C = CHCH2CH3
(d) CH3CH = CH – CH = CHCH3
9. The major product of the following reaction is
Online 2017 SET (2)
(a) (b)
 14. The major product of the following reaction is :
Online 2019 SET (2)

(a) (b)

10. The increasing order of reactivity of the following (c) (d)

halides for the SN1 reaction is
(2017) 15. The major product of the following reaction is
(I) CH3CH(Cl)CH2CH3 (II) CH3CH2CH2Cl
(III) p-H3CO–C6H4 – CH2Cl
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
(c) (I) < (III) < (II) (d) (II) < (III) < (I)
11. The major product of the following reaction is : (2018)

(a) (b)

(c) (d)

12. Which of the following will most readily given the

dehydrohalogenation product. Online 2018 SET (1)

(a) (b)
(2019-04-10/Shift-1)
16. Heating of 2-chloro-1-phenylbutane with EtOK/EtOH
gives X as the major product. Reaction of X with
(c) (d) Hg(OAc)2 / H 2 O followed by NaBH 4 gives Y as the
major product. Y is: (2019-04-09/Shift-2)
13. The total number of optically active compounds formed
in the following reaction is : Online 2018 SET (2)

(1) Two (2) Four

(3) Six (4) Zero
17. The major product of the following reaction is

(2019-01-09/Shift-1)

(A)

19. Which of the following compounds will show retention

(B) in configuration on nucleophilic substitution by OH–
ion ? (2020-09-02/Shift-1)

(a) (b)

(C)

(c) (d)

(D)

20. The major product obtained from E2 – elimination of 3-

18. The major product of the following reaction is : bromo-2-fluoropentane is : (2020-09-02/Shift-2)
(2019-01-12/Shift-2)
 (a) (A) and (B) (b) (A), (B) and (C)
(c) (A) and (C) (d) (B) and (d)
23. The decreasing order of reactivity of the following
compounds towards nucleophilic substitution (SN2) is :

(2020-09-03/Shift-2)
(a) (III) > (II) > (IV) > (I) (b) (IV) > (II) > (III) > (I)
21. Consider the reaction sequence given below : (c) (II) > (III) > (IV) > (I) (d) (II) > (III) > (I) > (IV)
24. Among the following compounds, which one has the
shortest C – Cl bond? (2020-09-04/Shift-2)

(a) (b) H3C  Cl

Which of the following statements is true : (c) (d)

(2020-09-02/Shift-2)
(a) Changing the concentration of base will have no
effect on reaction (1). 25. The increasing order of the boiling points of the major
(b) Doubling the concentration of base will double the products A, B and C of the following reaction will be:
rate of both the reactions.
(c) Changing the base from OH– to –OR will have no
(1)
effect on reaction (2).
(d) Changing the concentration of base will have no
effect on reaction (2).
22. The mechanism of SN1 reaction is given as : (2)

(3)
(2020-09-06/Shift-2)
(a) 1 < 2 < 3 (b) 3 < 1 < 2
(c) 1 < 3 < 2 (d) 2 <3< 1
A student writes general characteristics based on the 26. Consider the following reactions:
given mechanism as :
(A) The reaction is favoured by weak nucleophiles.
(B) R would be easily formed if the substituents are
bulky.
(C) The reaction is accompanied by racemization.
(D) The reaction is favoured by non-polar solvents.
Which observations are correct ?
(2020-09-03/Shift-1)

Which of these reaction(s) will not produce Saytzeff
product?
(a) b and d (b) d only
(c) a, c and d (d) c only
27. For the following reactions,
(a) B > A > D > C (b) B >D>C>A
(c) B >D>A> C (d) D>B>C>A
Ans : (d)
Sol :
In E1mechanism, the rate determining step is formation
of carbocation. So, stability of carbocation formed
decides the rate.
In option D, the cation formed is resonance stabilised.
In option C, the cation formed is a 2o carbocation.
In option A and B, the carbocations formed are 1o but
there is a chance of rearrangement in option b and
after the rearrangement, the carbocation formed in
option b will be allylic. So, the order of reaction is as
(2020-01-7/Shift-1) follows:
D > B > C > A.
29. Which of the following reactions will not produce a
racemic product? (2020-01-09/Shift-2)

ks and ke, are, respectively, the rate constants for

ks
substitution and elimination, and 
ke , the correct
option is ______. (2020-01-07/Shift-2)

(a)  A   B and ke  A  ke  B 
(b) B   A and ke  A   ke  B 

(c)  A  B and ke  B   k e  A 

(d)  B   A and ke  B   ke  A
28. The decreasing order of reactivity towards
dehydrohalogenation (E1) reaction of the following
compounds is:

(2020-01-08/Shift-1)
 EXERCISE - 6 : PREVIOUS YEAR JEE ADVANCE QUESTIONS

1.
EXERCISE - 4 : PREVIOUS YEAR
Which of the following has the highest nucleophilicity ? 7. How many structures of F is possible ? (2003)
– JEE MAINS QUESTIONS
(2000)
–
(a) F (b) OH
(c) CH3 (d) NH 2
2. What would be the major product in each of the following
reactions ? (2000)
(a) 2 (b) 5
(c) 6 (d) 3
(i)
8. (2003)

(a) C6H5OC2H5 (b) C2H5OC2H5

(ii)
(c) C6H5OC6H5 (d) C6H5I
9. Among the following, the molecule with the highest dipole
moment is (2003)
(a) CH3Cl (b) CH2Cl2
(c) CHCl2 (d) CCl4
3. How would you synthesize 4-methoxyphenol from
bormobenzene in NOT more than five steps ? State clearly
the reagents used in each step and show the structures of
the intermediate compounds in your synthetic scheme.
(2001) 10. (2004)
4. An SN2 reaction of an asymmetric carbon of a compound
always gives (2001)
(a) an enantiomer of the substrate
(b) a product with opposite optical rotation
(c) a mixture of diastereomers
(d) a single stereoisomer
5. Cyclobutylbromide on treatment with magnesium in dry
ether forms an organometallic compound (A). The
organometallic reacts with ethanal to give an alcohol (B) Identify A to D .
after mild acidification. Prolonged treatment of alcohol (B)
with an equivalent amount of HBr gives 1-bromo-1- 11. The following compound on hydrolysis in aqueous acetone
methylcyclopentane (C). Write the structures of (A), (B) will give (2005)
and explain how (C) is obtained from (B). (2001)
6. Identify the set of reagents/reaction conditions X and Y in
the following set of transformations (2002)

(K)
(a) X = dilute aqueous NaOH, 20°C, Y = HBr/acetic acid,
20°C
(b) X = concentrated alcoholic NaOH, 80°C, Y = HBr/acetic
acid, 20°C
(c) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C (L)
(d) X = concentrated alcoholic NaOH, 80°C, Y = Br2/
CHCl3, 0°C
 15. List-I contains reactions and List-II contains major products.
(2018)
(M) List-I List - II

(P)  1.
(a) mixture of (K) and (L)
(b) mixture of (K) and (M)
(c) only (M) (d) only (K) (Q) 2.
12. When phenyl magnesium bromide reacts with t-butanol, the
product would be (2005)
(a) benzene (b) phenol (R) 3.
(c) t-butyl benzene (d) t-butyl phenyl ether
13. The major product of the following reaction is (2008)
(S) 4.

5.
Match each reaction in List-I with one or more products in
List-II and choose the correct option.
(a) P - 1,5; Q - 2; R - 3; S - 4
(b) P - 1,4; Q - 2; R - 4; S - 3
(c) P - 1,4; Q - 1, 2; R - 3,4; S - 4
(d) P - 4,5; Q - 4; R - 4; S - 3,4

(a) (b)

(c) (d)

14. The correct statements for the following addition reactions

is (are) (2017)

(a) (M and O) and (N and P) are two pairs of enantiomers

(b) Bromination proceeds through trans-addition in both the
reactions
(c) O and P are identical molecules
(d) (M and O) and (N and P) two pairs of diastereomers
 ANSWER KEYS
EXERCISE # 1
1. (B) 2. (B) 3. (B) 4. (C) 5. (C) 6. (A) 7. (A)

8. (A) 9. (B) 10. (C) 11. (C) 12. (C) 13. (B) 14. (C)

15. (C) 16. (C) 17. (A) 18. (D) 19. (A) 20. (A) 21. (C)

22. (C) 23. (B) 24. (A) 25. (A) 26. (A) 27. (C) 28. (B)

29. (B) 30. (B) 31. (A) 32. (C) 33. (A) 34. (C) 35. (A)

36. (A) 37. (C) 38. (D) 39. (B) 40. (B) 41. (B) 42. (A)

43. (C) 44. (C) 45. (C) 46. (A) 47. (A) 48. (B) 49. (D)

50. (B) 51. (A) 52. (B) 53. (B) 54. (C) 55. (B) 56. (C)

57. (D) 58. (B) 59. (D) 60. (C) 61. (C) 62. (B) 63. (A)

64. (B) 65. (B) 66. (C) 67. (B) 68. (D) 69. (B) 70. (C)

71. (B) 72. (D) 73. (B) 74. (B) 75. (A) 76. (A) 77. (D)

78. (B) 79. (C) 80. (C) 81. (A) 82. (C) 83. (D) 84. (A)

85. (B) 86. (A) 87. (C) 88. (B) 89. (B) 90. (C) 91. (A)

92.* (BD) 93.* (ABD) 94. (A) 95. (B) 96. (C) 97. (C) 98. (A)

99. (A) 100. (B)

EXERCISE # 2
1. (B) 2. (B) 3. (C) 4. (A) 5. (C) 6. (A) 7. (A)

8. (D) 9. (C) 10. (A) 11. (C) 12. (D) 13. (B) 14. (A)

15. (B) 16. (B) 17. (A) 18. (D) 19. (A) 20. (D) 21. (A)

22. (A)
EXERCISE # 3
1. (C) 2. (A) 3. (B) 4. (A) 5. (C) 6. (B) 7. (A)

8. (C) 9. (A) 10. (B) 11. (C) 12. (B) 13. (D) 14. (C)

15. (A) 16. (A) 17. (B) 18. (C) 19. (D) 20. (D) 21. (B)

22. (A) 23. (A) 24. (A) 25. (A) 26. (D) 27. (B) 28. (B)

29. (B)
EXERCISE # 4
1. (ABD) 2. (BD) 3. (ABC) 4. (AB) 5. (BC) 6. (B) 7. (AB)

8. (A) 9. (A) 10. (B) 11. (D) 12. (D) 13. (A)
14. A  S; B  R; C  Q; D  P 15. A  T; B  S; C  R; D  Q; E  P

16. A  P, Y; B  Q, X; C  R, W 17. A  S; B  R; C  Q; D  P

18. AR;BQ;CP 19. AP;BQ;CR;DP

20. AS;BQ;CR;DP 21. A2;B1;C4;D3

22. AS;BR;CQ;DP 23. AS;BQ;CP;DR

24. (B) 25. A  W ; B  XY ; C  WY ; D  Z

26. A  P ; B  Q, S ; C  Q, R ; D  R, S 27. AP;BR;CQ;DT

28. AS;BS;CP;DS

29.

EXERCISE # 5
PREVIOUS YEAR JEE MAINS QUESTIONS
1. (a) 2. (a) 3. (b) 4. (b) 5. (d) 6. (a) 7. (b) 8. (d)

9. (b) 10. (b) 11. (d) 12. (d) 13. (b) 14. (b) 15. (a) 16. (a)

17. (a) 18. (b) 19. (a) 20. (a) 21. (a) 22. (b) 23. (c) 24. (d)

25. (d) 26. (d) 27. (c) 28. (d) 29. (b)

EXERCISE # 6
PREVIOUS YEAR JEE ADVANCE QUESTIONS
1. (c)
2. i
CH 3
|
CH 3  C  CH  CH 3

(ii)
3.

4. (d)

5.

6. (b) 7. (d) 8. (b) 9. (a)

10.

11. (a) 12. (a) 13. (a) 14. (b,d) 15. (b)